We report here a comparative study of the effects of La-substituted Ca on (Bi, Pb):2212 and (Bi, Pb):2223 superconductors with various La content (0.00 ≤ x ≤ 0.30). Regardless of the effects of La, it is evident that the superconducting volume fraction, excess of oxygen, critical concentration for quenching superconductivity, Vickers hardness, anisotropy, interlayer coupling, critical magnetic fields, and critical current were higher for the 2212 series than the 2223 series. In contrast, orthorhombic distortion, c-parameter, crystallite diameter, doping distance, distance between two Cu atoms, hole carrier/Cu ion ratio, melting temperature Tm, critical temperature Tc, onset of diamagnetic TcM, surface energy, elastic component, resistance pressure, and c-axis coherence length were higher for the 2223 series than the 2212 series. An inverse linear relationship between Tm and Tc was estimated for both series, and for room-temperature (RT) bismuth–strontium–calcium–copper–oxide (BSCCO) superconductors, the required Tm values should be 1048.03°C for the 2223 series and 784.48°C for the 2212 series. Surprisingly, the difference in temperature between zero resistivity and diamagnetic onset |TcM − TcR| for La = 0.30 samples is 30 K. In the critical field region (CFR), the exponents of order parameters (OPD) are two-dimensional (2D), but their values were higher for the 2212 series than the 2223 series. Further, they became three-dimensional (3D) as La increased to 0.30 due to the reduced effective length in highly substituted samples. Our results were discussed with the help of the differences in the physical parameters between the considered series. These findings revealed that the 2212 series is more suitable for applications that need higher hardness and critical fields and currents. In contrast, the 2223 series is more suitable for research for higher Tc and altering plastic deformation. To our knowledge, the present systematic investigation has not been reported elsewhere, which highlights the present work.